1-phenylazo-2,3-hydroxynaphtholic acid phenyl amide containing a sulfonic acid imido-ureide group

ABSTRACT

PIGMENTS OF THE MONOAZO SERIES WHICH CONTAIN A NUCLEARLY BOUND SULFONIC ACID IMIDO-UREIDE GROUP ARE USEFUL FOR THE COLORATION OF PLASTICS, TEXTILES, PAPER, NATURAL RESINS AND RUBBER.

United States Patent 01 lice 3,598,803 Patented Aug. 10, 1971 US. Cl. 260-204 8 Claims ABSTRACT OF THE DISCLOSURE Pigments of the monoazo series which contain a nuclearly bound sulfonic acid timido-ureide group are useful for the coloration of plastics, textiles, paper, natural resins and rubber.

DESCRIPTION This invention relates to pigments of the monoazo series which contain a substituted sulphonic acid amide group in the molecule and to the production of these pigments and their use for the coloration of plastics, textiles, paper, natural resins and rubber.

These pigments have the formula R1 X H (I) where D stands for the radical of a diazo component of the aromatic or heterocyclic series, B for the radical of a coupling component, R for a hydrogen atom, a hydrocarbon radical which may be substituted, or an acyl radical, R for a hydrogen atom or for a radical of the formula -CNR1 X for an oxygen or sulphur atom or for the =NH group,

and n for 1 or 2, and where the molecule is free from carboxylic acid and sulphonic acid groups.

These compounds are produced by diazotizing a diazo compound of formula and coupling the resulting diazonium compound with a coupling component of formula I-IE (III) wherein the radical D of (II) or the radical E of (HI) bears a group of formula The preferred radicals D in the diazo components are phenyl radicals which may be substituted if desired. Phenyl, naphthyl or pyrazolone radicals, which likewise may be substituted, are examples of E radicals. These radicals may bear any desired non-water-solubilizing substituents, in particular those commonly present in pigments, for example halogen atoms, notably chlorine or bromine atoms, alkyl or alkoxy groups of lower molecular weight, i.e. those containing 1 to 4 carbon atoms, hydroxyl, amino, aryl, aryloxy, acyl, acylamino, carboxylic acid ester, cyano or nitro groups, or N-substituted carboxylic acid amide or sulphonic acid amide groups. All the hydrocarbon substituents may themselves be substituted, for example by halogen atoms, hydroxyl or cyano groups.

The acyl groups may be radicals of formula R--X or R'Y, where R stands for a hydrocarbon radical which may bear non-water-solubilizing substituents and/or may contain hetero atoms, X for -OCO or SO R for a hydrogen atom or R, Y for CO-, NR"CO or NR"SO and R for a hydrogen atom or R.

Hydrocarbon radicals of prime interest are lower alkyl radicals, i.e. those bearing 1 to 4 carbon atoms, and phenyl radicals, which may contain any of the aforecited substituents.

The preferred pigments have the formula In these formulae the benzene nuclei A and B may bear any desired non-water-solubilizing substituents, for instance the aforementioned ones. They are produced by diazotizing an amine of formula H X H and coupling the resulting diazonium compound with a compound of formula (V III) onto 0 CHzC 0 NH@ The coupling reaction is conducted in the normal manner in a weakly acid, neutral or alkaline medium at room temperature or with cooling.

The new compounds have outstanding properties as pigments. They are virtually insoluble in the commonly used solvents and have very good rheological properties. Applications for which they are suitable include the dyeing of paper stock, the mass coloration of plastics in solution or other forms, the coloration of natural and synthetic resins and rubber, and the printing of textiles and paper.

It is of advantage to prepare the pigments in paste form before application. For this purpose they are submitted to mechanical treatment in ball or roller mills or other suitable equipment and if necessary in the presence of dispersing agents, such as the condensation products of naphthalenesulphonic acids and formaldehyde. The pigment pastes can be used for pigmentation in the paste form as obtained, or they can be dried and the resulting powders ground.

In the aforenamed materials the pigments are outstandingly resistant to migration and fast to light, and have very goodfastness to washing, chlorine, hypochlorite and peroxide bleaching, cross dyeing, blind vats, hydrosulphite, dry cleaning, rubbing, overlacquering and solvents. They show good transparency and heat stability.

The parts and percentages given in the examples are by weight and the temperatures are in degrees centigrade.

EXAMPLE 1 2.4- parts of 1-amino-2-methoxybenzene-S-sulphonic acid-imidoureide are dissolved in 300 parts of Water and 38 parts of 30% hydrochloric acid. The solution is cooled to and 20 parts of a S-normal solution of sodium nitrite are added for diazotization. When the diazonium salt solution has formed, it is allowed to run slowly at 20 into a solution of 38 parts of 2-hydroxy-3(3'-chloro-4',6'-dimethoxyphenylaminocarbonyl)-naphthalene in 400 parts of ethanol, 800 parts of Water and 50 parts of 30% sodium hydroxide solution. On completion of the coupling reaction the batch is acidified with acetic acid, raised to 90 and filtered. The residue, a red pigment, is washed with water and dried at 60. It is resistant to migration in polyvinyl chloride and is fast to light in this and the other named materials. When the pigment is previously treated with heating in an organic solvent, for example mono-, dior tri-chlorobenzene, nitrobenzene, or, in particular, dimethyl formamide, it exhibits a more brilliant and intense shade in the pigmented or dyed material.

The l amino 2-methoxybenzene 5-sulphonic acid EXAMPLE 2 A diazonium salt solution is prepared with 24.4 parts of l-amino-Z-methoxybenzene-S-sulphonic acid imidoureide in accordance with the procedure of Example 1. It is dropped into a solution of 31.4 parts of 2-hydroxy- 3-(2'-methoxyphenylaminocarbonyl)-naphthalene in 400 parts of ethanol, 800 parts of water and parts of 30% sodium hydroxide solution. The reaction mixture is then acidified and raised to 90, and the product filtered off, washed with water and dried at It is a red pigment and has valuable properties, comparable to those of the product obtained by the procedure of Example 1.

The tabulated examples which follow, give the formulae of the diazo components and the R' groups of the coupling components of formula The components can be reacted as detailed in Example 1. Coupling with the diazonium compound takes place in position 1 of the naphthalene nucleus. The shade of the resulting pigments in polyvinyl chloride is noted in the last column of the table.

. Shade Example No. ilDiazo component R in PVC 33 CH; OCHQ Red.

-NH c1 .i lg CH5 i t l5 Or-N l-I-(F-N Ha INH t. dame as above tilH Bordeaux.

i -o1 WK-.-

i) CH Red.

i b Oz-NH-fi-NH-fi-NH:

INH NH t5 H \iBame as above Red.-

(f-NllU UNllg INII wwudu ltod;

s OzNEL-C-NH Shade Example No Diazo component R' in PVC 8 NH: .-.--d0 Red.

8 OzNH-(F-NH: H

9 IfHz .-...d0 Red.

| S OgNH-(fi-NH;

10 0 CH Red.

0 CH1 S Oz-NH-(fi-NHz 11 Same as above CH; Bordeaux.

12 CH; O OH Red.-

NHg -0 CH3 I S OaNHCNHC-NH2 NE NH 13 OCH; Same as above... Red.-

I S Or-NH-(IJNHC ONH:

14 NH: O CH: Red;

I S OzNH-(flJ-NH:

15 Same as above 0 CH Red;

16 NH, Red.

- O CH;

- S Oz-N I(|l-NH: 1

17 NH; Same as above Red.

Shade Example N0. Dlazo component 3'' h YC S 02NH-(|3NH2 19 IYH S O2-NH-(3-NHz 20 NF'I:

S O2NH(HJ-NH Ink mnflo ma.

Med.

0cm liked-brown.

\Bamo as above IJDo.

.... ..do-....-.-...---......- NBrown.

M....Mo.... -Q Red-brown:

m CH; 11mm;

Shade Example No. Diazo component R in PVC 26 (3H3 Same as above V. Red.

NHz

S Or-NH-(fll-NHQ 27 NH: ""110 Rad.

5 Oz-NH-F-NH:

28 NH2 -....(10 Red.

S Or-NH--fi1-NH2 29 IIIH: ----.d0 Red.

8 O2-NH-?l3-NH2 30 Same as above (RCH; Red.

g CH3 #1 fi 0 CH3 Red.

32 IIIH: 0 CH: Bordeaux.

OCH; C?-o CH: CHzO- l I S Oa-NH-CNH2 33 NH: Red.

S OzNHfi!-NH:

| S Or-NH-fiE-NH:

34 O CH; Same as above Red.

The. components listed in the following table can likewise be reacted as described in Example 1 to give excellent pigments.

V Shade Example No. Diazo component Coupling component I in PVC 44. IIIH 7 Yellow.

CH; O OH:

CHaCOCHzCONH- O1 cmo- I O CH S OzNH-]JNH 45 11111: Same as above .M D0.

S OzNHfi7'NH2 46 CH3 -.-..\'10 D0 I S OaNH-fiJ-NH:

Formulae of representative dyestulfs of the foregoing OOHS examples are as follows: 40 l (IXJHs CH3 H0 CO-NH CH m m-NHQOCHa N: om

N=N Cl S O2-NH--(.I7-NH sio NH c NH NH r L 2 Example 35 Example 7 OCH;

$ on; HO 0 0-NH 01 SO -NH-C-NH; H

II Example 3 ExampleQ Having thus disclosed the invention what we claim is: 0 CH 1. A20 dyestuif of the formula B t H 0 CI, ONH OCH3 D N:N E

6 wherein D is unsubstituted phenyl or phenyl substituted by at 7 least one member selected from the group consisting O of chlorine, bromine, methyl, methoxy, lower alkyl sulphonic acid amide and m groups of the formula N H -s O -NH-C-NH-R Example 18 15 E is a coupling component of the formula on ONHB where the free valency bond leads directly to a nitrogen of the azo bridge;

B is a member selected from the group consisting of unsubstituted naphthyl, and phenyl substituted by at least one member selected from the group consisting of chlorine, bromine, methyl methoxy and n groups of the formula m is or 1,

n is 0 or 1 and the sum of m-I-n is at least one;

R is hydrogen or a group of the formula x is oxygen or =NH.

2. Monoazo dyestufi' according to claim 1 wherein X is the =NH group.

3. Dyestuff according to claim 2 of the formula wherein any further substituent on nucleus A is a member selected from the group consisting of chloro, bromo, methyl, methoxy and dimethylaminosulfonyl and any substituent on nucleus B is a member selected from the group consisting of chloro, bromo, methyl and methoxy.

4. The dyestuff according to claim 3 of the formula 1 O-NH-Q-DCH: m

7. The dyestufi according to claim 3 of the formula 8. The dyestuff according to claim 3 of the formula iii 02-NHiCNHg References Cited UNITED STATES PATENTS 2,367,072 11/ 1945 Thurston 260-207X 2,367,073 1/1945 Thurston 260-207X 2,920,070 11/1960 Jirou et a1. 260-207X 3,096,356 7/1963 Jirou et a1. 260-192X 3,260,713 7/1966 St. Alban 260-207X FOREIGN PATENTS 785,672 10/1957 Great Britain 260-204 1,392,484 1965 France 260-192 CHARLES B. PARKER, Primary Examiner C. F. WARREN, Assistant Examiner us. 01 x 1 

